Laser pulse length dependence of internal energy transfer in UV-MALDI-MS

Recent internal energy (IE) measurements for various analytes in matrix-assisted laser desorption ionization (MALDI) have indicated that the amount of IE transferred to analytes not only depends on the matrix but also on the nature of the analyte. Common matrixes, such as α-cyano-4-hydroxycinnamic acid (CHCA), 3,5-dimethoxy-4-hydroxycinnamic acid (sinapinic acid, SA), and 2,5-dihydroxy-benzoic acid (DHB), had been characterized as “cold” or “hot” according to the IEs of analyte ions produced in the corresponding MALDI plume. In this contribution, we present evidence that IE transfer in MALDI depends on the matrix, analyte, as well as on the laser pulse properties. A substituted benzylpyridinium salt as a thermometer molecule (TM) was investigated in CHCA, SA, and DHB matrixes. A nitrogen laser (4 ns pulse length) and a mode locked frequency tripled Nd:YAG laser (22 ps pulse length) were used as excitation sources at various fluences. Survival yields (SYs) of the analyte molecular ions were extracted from the spectra and the corresponding IEs were obtained from Rice–Ramsperger–Kassel–Marcus (RRKM) theory. The SYs indicate that the IEs of analyte ions in MALDI are analyte, matrix, and laser source dependent. The ion generation threshold fluences follow the same order for both lasers: CHCA<SA<DHB, but for the analyte the mode locked 3×ω Nd:YAG laser source requires a higher threshold fluence than the nitrogen laser. Despite the higher fluence, the SYs are generally higher (the corresponding IEs are lower) for the 3×ω Nd:YAG laser than for the nitrogen laser. The SYs of the TM molecular ions decrease with an increase of fluence for both the ns laser and the ps laser.